Photochemical singlet oxygen generations having enhanced singlet oxygen yields

ABSTRACT

The invention relates to photochemical singlet oxygen generators useful as bleaching agents or anti-microbial agents in laundry detergent compositions or in hard surface cleaning compositions. The singlet oxygen generators described herein have enhanced singlet oxygen generation due to aromatic moieties teed to the molecules, said aromatic moieties absorbing ultra violet radiation then re-emitting the radiation as fluorescence at a wavelength absorbable by the singlet oxygen producing photosensitizer unit. The increase in the number of photons having an absorbable wavelength provides an increase in the production of singlet oxygen.

This Applications Claims priority from U.S. Provisional Applications No.60/035,904 filed Jan. 24, 1997.

FIELD OF THE INVENTION

The present invention relates to photochemical singlet oxygen generatorshaving a photon harvester moiety which enhances the singlet oxygen yieldof the generator without adversely affecting the remaining properties ofthe molecule. The photochemical singlet oxygen generators describedherein are useful in laundry detergent compositions or hard surfacecleaning compositions as bleaching agents or anti-microbial agents. Thepresent invention also relates to methods for bleaching fabrics andcleaning hard surfaces with the photochemical singlet oxygen generators.

BACKGROUND OF THE INVENTION

It is known that certain water soluble phthalocyanine andnaphtalocyanine, mixed cyanine and metallocyanine compounds can be usedas photobleaching and anti-microbial agents. Phthalocyanines andnaphthalocyanines or their metal complexes can form “singlet oxygen”.

Singlet oxygen can be formed by chemical as well as photochemicalprocesses. Singlet oxygen is a highly oxidative species capable ofreacting with substances, for example, with stains on a fabric to bleachthem to a colorless and usually water-soluble state. There are manyexamples of phthalocyanines and naphthalocyanines photobleaches, themost common being the zinc and aluminum phthalocyanines. In theliterature the term “photosensitizer” is often used instead of“photoactivator” and may therefore be considered as standing equallywell for the latter term used throughout this specification

The prior art teaches phthalocyanine and naphthalocyanine compoundshaving the general structure

where Me is a tnansition or non-transition metal, (Sens.) is aphthalocyanine or naphthalocyanine ring which, when combined with asuitable Me unit, is capable of undergoing photosensitization of oxygenmolecules, R units are substituent groups which are bonded to thephotosensitization ring units (Sens.) to enhance the solubility orphotochemical properties of the molecule, and Y units are substituentsassociated with the metal atom, for example, anions to provideelectronic neutrality.

It has been a task of formulators of photobleaches to modify theproperties of the (Sens.) unit of the molecule to increase the quantumefficiency and/or the water solubility. Typically this has beenaccomplished by substitution on the photochemical (Sens.) ring. However,substituents that improve one property may have a negative effect on theother. Consequently it has proven difficult to provide photobleacheswhich are water soluble and efficient.

Surprisingly, it has been found that the compounds of the presentinvention allow formulators to increase the photoefficiency of thesinglet oxygen generators while being able to maintain the otherparameters of the molecule. In addition, the solubility of thephotochemical singlet oxygen generator can be modified without producingan undesired effect in the photophysics of the molecule. This ability todelineate and selectively modify the key structural elementscontributing to the target properties of the molecule allows theformulator to proceed without having to rely upon a “hit and miss”stratagem.

The present invention provides a means by which an effectivephotosensitizer can have its efficiency increased without risking aconcomitant loss of other desired properties inter alia solubility orcolor. This task is achieved by attaching a photon “harvester” moiety tothe singlet oxygen generator. This harvester absorbs ultra violet lightand transfers the energy to the photosensitizer portion of the moleculevia a process known to those of skill in the art as “Foster EnergyTransfer”. This harvester group must be within a critical distance tofacilitate this energy transfer. This energy transfer acts to increasethe effective number of photons absorbed by the photosensitizer unitand, as photons are “consumed” in producing singlet oxygen, an increasetherefore in singlet oxygen generation.

It is therefore an object of the present invention to providephotochemical singlet oxygen generators which serve as photobleaches andphotodisinfectants and which have a higher efficiency in producingsinglet oxygen. It is a further object of the present invention toprovide photobleaching compositions suitable for use as laundrydetergent bleaching compositions.

It is a yet further object of the present invention to provide enhancedphotobleaching hard surface cleaning compositions for non-porous hardsurfaces, inter alia, Formica®, ceramic tile, glass, or for porous hardsurfaces such as concrete or wood.

It is a still further object of the present invention is to provide amethod for bleaching fabric with laundry compositions comprising thephotobleaching compounds of the present invention

It is yet still a further object of the present invention is to providea method for cleaning hard surfaces with the photobleaching compounds ofthe present invention.

BACKGROUND ART

Various patent documents relate to photochemical bleaching or to the useof cyanine compounds as well as their formulation and synthesis. See forexample U.S. Pat. No. 3,094,536 issued Jun. 18, 1963; U.S. Pat. No.3,927,967 issued Dec. 23, 1975; U.S. Pat. No. 4,033,718 issued Jul. 5,1977; U.S. Pat. No. 4,166,718 issued Sep. 4, 1979; U.S. Pat. No.4,240,920 issued Dec. 23, 1980; U.S. Pat. No. 4,255,273 issued Mar. 10,1981; U.S. Pat. No. 4,256,597 issued Mar. 17, 1981; U.S. Pat. No.4,318,883 issued Mar. 9, 1982; U.S. Pat. No. 4,368,053 issued Jan. 11,1983; U.S. Pat. No. 4,497,741 issued Feb. 5, 1985; U.S. Pat. No.4,648,992 issued Mar. 10, 1987; and U.K. Pat. App. 1,372,035 publishedOct. 30, 1974; U.K Pat. App. 1,408,144 published Oct. 1, 1975; U.K. PatApp. 2,159,516 published Dec. 4, 1985; E.P. 285,965 A2; E.P. 381,211 A2published Aug. 8, 1990; E.P. 484,027 A1 published May 6, 1992; WO91/18006 published Nov. 28, 1991 and Japanese Kokai 06-73397 DerwentAbst. No. (94128933) published Mar. 15, 1994.

In addition to the above cited patent publications, other referencesdescribing the synthesis, preparation and properties of cyanines,incorporated herein also by reference; Phthalocyanines: Properties andApplications, Leznoff, C. C. and Lever A. B. P. (Eds), VCH, 1989;Infrared Absorbing Dyes, Matsuoka, M. (Ed), Plenum, 1990; Inorg. Chem.,Lowery, M. J. et al., 4, pg. 128, (1965); Inorg. Chem. Joyner R. D. etal., 1, pg. 236, (1962); Inorg. Chem., Kroenke, W. E. et al., 3, 696,1964; Inorg. Chem. Esposito, J. N. et al., 5, pg.1979, (1966); J. Am.Chem. Soc. Wheeler, B. L. et al., 106, pg. 7404, (1984); Inorg. Chem.Ford, W. E, et al., 31, pg. 3371, (1992); Material Science, Witkiewicz,Z. et al., 11, pg. 39, (1978); J. Chem. Soc. Perkin Trans. I, Cook, M.J., et al., pg. 2453, (1988); J. Chin. Chem. Soc., 40, pg. 141, (1993);J. Inorg. Nucl Chem., 28, pg. 899, (1966); Polymer Preps, 25, pg. 234,(1986); Chem. Lett., 2137, (1990); J. Med. Chem., 37, pg. 415, (1994).

SUMMARY OF THE INVENTION

The present invention relates to singlet oxygen generators useful as ableaching agent or disinfectant in laundry detergent compositions andhard surface cleaning compositions, said singlet oxygen generatorshaving the formula:

wherein P is a photosensitizer unit; R is an axial moiety which mediatesthe solubility or substantivity of the singlet oxygen generator, and Dis a unit which increases the efficiency of singlet oxygen production,said unit having the formula

—L¹—E

or

—L¹—B—[L²—E]_(m)

wherein E is an aromatic unit, provided said E aromatic unit:

a) absorbs ultra violet radiation at a wavelength of from about 200 nmto about 400 nm;

b) has an extinction coefficient of at least about 100; and

c) has a fluorescence spectrum which overlaps an absorption band of saidphotosensitizer unit;

B is a branching unit; and L¹ and L² are linking units, provided saidlinking units when taken together with said B unit comprise a total ofat least 20 continuous covalent bonds from said P unit to said E units;m is from 2 to 4.

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All temperatures are in degrees Celsius (°C.)unless otherwise specified. All documents cited are in relevant part,incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to photochemical singlet oxygen generatorswhich have an enhanced chromophoric groups. This increase inphotoefficiency is due to the presence of a photon “harvester” moietywhich is capable of broadening the electromagnetic radiation utilized bythe photosensitizing unit in the production of singlet oxygen

The present invention also relates to cleaning compositions whichcomprise the photochemical singlet oxygen generators of the presentinvention. Laundry detergent compositions according to the presentinvention comprise:

a) at least about 0.1%, preferably from about 0.1% to about 30%, morepreferably from about 1% to about 30%, most preferably from about 5% toabout 20% by weight, of a detersive surfactant wherein the detersivesurfactant is selected from the group consisting of anionic, cationic,nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof;

b) at least about 0.001 ppm, preferably from about 0.01 to about 10000ppm, more preferably from about 0.1 to about 5000 ppm, most preferablyform about 10 to about 1000 ppm, of a singlet oxygen generator havingthe formula:

 wherein P is a photosensitizer unit; R is optionally an axial moietywhich mediates the solubility or substantivity of the singlet oxygengenerator; and D is a unit which increases the efficiency of singletoxygen production, said unit having the formula

—L¹—E

 or

—L¹B—[L²—E]_(m)

 wherein E is an aromatic unit, provided said E aromatic unit:

i) absorbs ultra violet radiation at a wavelength of from about 200 nmto about 400 nm;

ii) has an extinction coefficient of at least about 100; and

iii) has a fluorescence spectrum which overlaps an absorption band ofsaid photosensitizer unit;

 B is a branching unit; and L¹ and L² are linking units, provided saidlinking units when taken together with said B unit comprise a total ofat least 20 continuous covalent bonds from said P unit to said E units;m is from 2 to 4; and

c) the balance carriers and adjunct ingredients, said adjunctingredients are selected from the group consisting of buffers, builders,chelants, filler salts, soil release agents, dispersants, enzymes,enzyme boosters, perfumes, thickeners, abrasives, solvents, clays, andmixtures thereof

Photosensitizing Units, P

The photosensitizers of the present invention suitable for use asphotobleaches and photodisinfectants comprise cyanine rings as well ashybrid cyanine rings. The cyanine rings are those formed from fouridentical aromatic units, for example, phthalocyanines andnaphthalocyanines. The hybrid rings are formed by chemically reactingtogether at least two different aromatic monomer units capable offorming a cyanine ring. Typically, cyanine rings are defined by the typeof aromatic monomer unit used to synthesize the target macrocyclic ring,for example, phthalocyanines are formed from derivatives of benzene,naphthalocyanines are formed from derivatives of naphthalene, etc.

The cyanine rings of the present invention have the general formula

wherein A, B, C, and D represent aromatic rings. For the purposes of thepresent invention these aromatic rings are preferably substituted orunsubstituted benzene, 1,2-naphthylene, 2,3-naphthalene, anthracene, andphenanthrene. However, this list is not meant to be inclusive orexclusive of any other aromatic ring capable of insertion into thecyanine ring including aromatic heterocyclic rings inter alia quinolinesor isoquinolines.

For the purpose of further illustrating the formation of hybrid cyaninerings useful for preparing the singlet oxygen generators of presentinvention, the scheme below depicts the expected mixture of cyaninerings obtained when the cyanine ring forming monomers,1,6dimethoxy-3,4-dicyanobenzene and 1,6-dibromo-3,4-dicyanobenzene, arereacted together under suitable conditions.

Reacted together under suitable conditions yield:

Other examples include but are not limited to the reaction oforthodicyanobenzene and 2,3dicyanonaphthalene as shown below

or the reaction of the corresponding phthalimidines as shown below

to yield the mixture of hybrid cyanines I-VI shown below.

For the purposes of the present invention ring components derived fromsubstituted and unsubstituted benzene can be written in either of twoequivalent resonance formulas:

wherein R¹, R², R³ and R⁴ are each independently selected from thesubstituents described herein below.

For the purposes of the present invention ring components derived fromsubstituted and unsubstituted 2,3-naphthylene can be written in eitherof two equivalent resonance formulas:

wherein R¹, R², R³, R⁴, R⁵, and R⁶ are independently selected from thesubstituents described herein below.

For the purposes of the present invention ring components derived fromsubstituted and unsubstituted 1,2-naphthylene can be written in eitherof two equivalent resonance formulas:

wherein R¹, R², R³, R⁴, R⁵, and R⁶ units are independently selected fromthe substituents listed herein below.

For the purposes of the present invention ring components derived fromsubstituted and unsubstituted 2,3-naphthylene can be written in eitherof two equivalent resonance formulas:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ units are independentlyselected from the substituents described herein below.

For the purposes of the present invention ring components derived fromsubstituted and unsubstituted phenanthrene can be written in either oftwo equivalent resonance formulas:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ units are independentlyselected from the substituents described herein below.

Each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ unit is independently:

a) hydrogen,

b) halogen;

c) hydroxyl;

d) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branchedalkenyl;

e) halogen substituted C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂alkenyl, C₃-C₂₂ branched alkenyl;

f) polyhydroxyl substituted C₃-C₂₂ alkyl;

g) C₁-C₂₂ alkoxy, preferably C₁-C₄ alkoxy, more preferred methoxy;

h) branched alkoxy having the formula

 wherein Z is hydrogen, hydroxyl, C₁-C₃₀ linear alkyl, C₁-C₃₀ branchedalkyl, C₁-C₃₀ alkoxy, —CO₂H, —OCH₂CO₂H, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, —PO₃ ²⁻M,—OPO₃ ²⁻M, and mixtures thereof; M is a water soluble cation insufficient amount to satisfy charge balance; x is 0 or 1, each yindependently has the value from 0 to 6, preferably from 0 to 6; each zindependently has the value from 0 to 100, preferably from 0 to about10, more preferably from 0 to about 3;

i) substituted aryl, and unsubstituted aryl having the formula:

 wherein R¹³ and R¹⁴ are independently selected from the groupconsisting of hydrogen, C₁-C₆ alkyl, C₃-C₆ alkenyl, C₁-C₆ alkoxy, C₃-C₆branched alkoxy, halogen, —CO₂ ⁻M⁺, —SO3⁻M⁺, —OSO₃ ⁻M⁺, —N(R¹⁵)₂, and—N⁺(R¹⁵)₃X⁻ wherein each R¹⁵ is independently hydrogen or C₁-C₄ alkyl;and mixtures thereof, preferably hydrogen C₁-C₆ alkyl, —CO₂ ⁻M⁺, —SO₃⁻M⁺, —SO₃ ⁻M⁺, and mixtures thereof, more preferably R¹³ or R¹⁴ ishydrogen and the other moiety is C₁-C₆ alkyl; wherein M is a watersoluble cation and X is a water soluble anion.

j) substituted alkylenearyl and unsubstituted alkylenearyl having theformula:

 wherein R¹³ and R¹⁴ are as defined above, p is from 1 to about 10.

k) substituted aryloxy and unsubstituted aryloxy having the formula:

 wherein R¹³ and R¹⁴ are as defined above.

1) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl unitsare defined as moieties having the formula:

 wherein R¹³ and R¹⁴ are as defined above, q is from 0 to about 10.

m) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl havingthe formula:

 wherein R¹³ and R¹⁴ are as defined above, w is from about 1 to about10.

n) C₁-C₂₂ linear C₃-C₂₂ branched thioalkyl, C₁-C₂₂ linear, C₃-C₂₂branched substituted thioalkyl, and mixtures thereof;

o) ester units of the formula —CO₂R⁹ wherein R⁹ is C₁-C₂₂ alkyl, C₃-C₂₂branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, all of whichcan be substituted with halogen; poly-hydroxyl substituted C₃-C₂₂ alkyl,C₃-C₂₂ glycol; C₁-C₂₂ alkoxy, C₃-C₂₂ branched alkoxy; substituted andunsubstituted aryl, alkylenearyl, aryloxy, oxyalkylenearyl,alkyleneoxyaryl; preferably C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, andmixtures thereof;

p) alkyleneamino units having the formula:

 wherein R¹⁰, and R¹¹ are each a C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl,C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, R¹² is hydrogen, C₁-C₂₂ alkyl,C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl andmixtures thereof, the index v is 0 or 1; X is a other water solubleanion, u is from 0 to 22, preferably u is from 3 to about 10. Examplesof water soluble anions include organic species such as fumarate,tartrate, oxalate and the like, inorganic species include chloride,bromide, sulfate, hydrogen sulfate, phosphate and the like;

q) an amino unit of the formula

—NR¹⁷R¹⁸

 wherein R¹⁷ and R¹⁸ are each a C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl,C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof;

r) alkylethyleneoxy units having the formula:

—(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z

 wherein Z is hydrogen, hydroxyl, —CO₂H, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, C₁-C₆alkoxy, substituted and unsubstituted aryl, substituted andunsubstituted aryloxy; alkyleneamino as defined herein above; ormixtures thereof; A units comprise nitrogen or oxygen, preferablyoxygen; M is a water soluble cation; v is 0 or 1; x is from 0 to 100,preferably from 0 to 20, more preferably from 0 to 5; y is from 0 to 12,preferably from 1 to 4; however, no peroxide —O—O— bonds are containedwithin the photobleaching compounds of the present invention;

s) siloxy and substituted siloxy of the formula —OSiR¹⁹R²⁰R²¹ whereineach R¹⁹, R²⁰, and R²¹ is independently selected from the groupconsisting of C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof, substituted orunsubstituted aryl, aryloxy; alkylethyleneoxy units of the formula:

—(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z

 wherein Z is hydrogen, hydroxyl, C₁-C₃₀ alkyl, —CO₂H, —SO₃ ⁻M⁺, —OSO₃⁻M⁺, C₁-C₆ alkoxy; substituted or unsubstituted aryl, and aryloxy;alkyleneamino as defined herein above, and mixtures thereof, preferablyhydrogen or C₁-C₆ alkyl, more preferably methyl; v is 0 or 1; x is from1 to 100, preferably from 0 to about 20, more preferably from 3 to about10; and y is from 0 to 12, preferably from about 0 to about 5.

Harvester Units, D

The photochemical singlet oxygen generators of the present inventioncomprise one or more “harvester units”. For the purposes of the presentinvention “harvester units” are defined as “units which increase theefficiency of singlet oxygen production by collecting un-usable energyin the form of ultra violet radiation then transfering said absorbedenergy to the photosensitizer unit of the singlet oxygen generator”.Typically, D units have the formula

—L¹—E

or

—L¹—B—[L²—E]_(m)

or

—L¹R

wherein E is an aromatic unit and R is the same as defined herein above.The requirements for an E unit according to the present invention are:

a) absorbs ultra violet radiation at a wavelength of from about 200 nmto about 400 nm;

b) has an extinction coefficient of at least about 100; and

c) has a fluorescence spectrum which overlaps an absorption band of saidphotosensitizer unit

By way of illustration and without limitation, examples of E units arenaphthalene, anthracene, p-terphenyl, and mixture thereof Harvester Dunits also comprise L¹ and L² linking units, wherein the L¹ and L² unitswhen taken together with a B unit comprise a total of at least 20continuous covalent bonds from said P unit to said E units; m is from 2to 4.

Preferred L¹ and L² units are independently selected from the groupconsisting of oxygen, linear or branched alkylene, linear or branchedalkenylene; linear or branched alkyleneoxy, substituted or unsubstitutedarylene, substituted or unsubstituted alkylenearylene, substituted orunsubstituted aryleneoxy, substituted or unsubstitutedoxyalkylenearylene, substituted or unsubstituted alkyleneoxyarylene, andmixtures thereof, defined herein further below.

For the purposes of the present invention an oxygen molecule may serveas a suitable L¹ unit, preferably when directly bonded to a branchingunit to form a moiety having the general formula:

For the purposes of the present invention linear or branched alkylenemoieties are defined as units having the formula:

wherein R¹⁶ is C₁-C₄ alkyl; the index i has the value from 1 to 30, theindex j has the value from 1 to 30. If only one linking group L¹ ispresent between the photosensitizer unit P and the harvester unit E thenthe value of i+j must be at least 20.

For the purposes of the present invention linear or branched alkenylenemoieties are defined as moieties comprising one or more units, orcombinations of units having the formula:

wherein R¹⁶ is C₁-C₄ alkyl; the index i has the value from 1 to 30. Inthe case where only one linking group L¹ is present between thephotosensitizer unit P and the harvester unit E then the values of i andj must be sufficient to provide at least 20 covalent bonds between saidphotosensitizer unit P and said harvester unit E.

For the purposes of the present invention linear or branched alkyleneoxymoieties which comprise the L¹ or L² units described herein below, aredefined as units or a combination of units having the formula:

wherein R¹⁶ is C₁-C₄ alkyl; the index x has the value from 2 to 4;whereas the values of the indices i, j and k must have sufficient valuefor at least 20 covalent bonds between the photosensitizer unit P andthe harvester unit E.

For the purposes of the present invention substituted or unsubstitutedarylene moieties are defined as 1,2-phenylene, 1,3-phenylene, and1,4-phenylene units having the formula:

wherein R¹⁶ is hydrogen, C₁-C₄ alkyl, and mixtures thereof. Aryleneunits may be used alone or in combination with other suitable moietiesto form L¹ and L² units.

For the purposes of the present invention substituted or unsubstitutedalkylenearylene moieties are defined as 1,2-phenylene, 1,3-phenylene,and 1,4-phenylene units having the formula:

wherein R¹⁶ is hydrogen, C₁-C₄ alkyl, and mixtures thereofalkylenearylene units may be used alone or in combination with othersuitable moieties to form L¹ and L² units.

For the purposes of the present invention substituted and unsubstitutedaryleneoxy moieties are defined as 1,2-phenyleneoxy, 1,3-phenyleneoxy,and 1,4-phenyleneoxy units having the formula:

wherein R¹⁶ is hydrogen, C₁-C₄ alkyl, and mixtures thereof. Aryleneoxyunits may be used alone or in combination with other suitable moietiesto form L ¹ and L² units.

For the purposes of the present invention substituted and unsubstitutedoxyalkylenearylene moieties are defined as 1,2-oxyalkylenephenylene,1,3-oxyalkylenephenylene, and 1,4-oxyalkylenephenylene units having theformula:

wherein R¹⁶ is hydrogen, C₁-C₄ alkyl, and mixtures thereof, the index whas the value from 1 to 30. Oxyalkylenarylene units may be used alone orin combination with other suitable moieties to form L¹ and L² units.

For the purposes of the present invention substituted and unsubstitutedalkyleneoxyarylene moieties are defined as 1,2-alkyleneoxyphenylene,1,3-alkyleneoxyphenylene, and 1,4-alkyleneoxyphenylene units having theformula:

wherein R¹⁶ is hydrogen, C₁-C₄ alkyl, and mixtures thereof, the index qhas the value from 1 to 30. Alkyleneoxyarylene units may be used aloneor in combination with other suitable moieties to form L¹ and L² units.

The D units of the present invention also optionally comprise branchingunits B said units having the formula:

wherein B is selected from the group consisting of boron, aluminum,nitrogen, phosphorous, carbon, silicon, tin, germanium, and mixturesthereof, preferably carbon or silicon, more preferably carbon.

Without wishing to be limited by theory, the “harvester groups”according to the present invention act to convert light energy of awavelength outside the absorption spectrum of the photosensitizer intoenergy which is transferred to the photosensitizing unit via a “FosterEnergy Transfer” which is a direct energy transfer process. Therefore bythis process the harvester units increase the photo efficiency of thephotosensitizing unit by first absorbing electromagnetic radiation inthe ultra violet spectral region then transfering this energy to thephotosensitizer unit. This process acts to “widen” or “expand” theabsorption spectra of the photosensitizer unit. In order to accomplishthis energy transfer the harvester groups of the present invention musthave their fluorescence emission bands at wavelengths in which thephotosensitizer unit absorbs light. Therefore some or all of thefluorescence emission spectrum of the E units must overlap theabsorption spectrum of the photosensitizer P units.

The aromatic moieties which comprise the E units of the presentinvention have extinction coefficients that are at least 100, preferablyat least 1000, more preferably at least 10,000.

Substantivity and Solubility Mediating Axial R units

The singlet oxygen generators of the present invention optionallycomprise an R unit. Substantivity and solubility mediating axial Runits, are bonded directly to the photoactive metal or non-metal atomwhich is chelated by the photosensitizing unit and occupies a positionaxial to the essentially planar photosensitizing unit. The utility ofeach R unit is primarily directed to the solubility or substantivityproperties of the compounds of the present invention. The selection ofan R unit can be made, in addition to, or in lieu of, solubilityrequirements, and be totally directed instead to the “substantivity” or“non-substantivity” of the compound. R units are nonionic, cationic, oranionic units.

For the purposes of the present invention the term “substantivity” isdefined as “the ability for a molecule to bind, adhere, or have ageneral affinity for a surface” inter alia fabric and hard surfaces.

The axial R units suitable for use as substantivity or solubilitymediation units of the present invention include:

a) hydrogen;

b) halogen;

c) hydroxyl;

d) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branchedalkenyl;

e) halogen substituted C₁-C₂₂ alkyl, C₃-C₂₂ branched allyl, C₂-C₂₂alkenyl, C₃-C₂₂ branched alkenyl;

f) polyhydroxyl substituted C₃-C₂₂ allyl;

g) C₁-C₂₂ alkoxy, preferably C₁-C₄ alkoxy, more preferred methoxy;

h) branched alkoxy having the formula

 wherein Z is hydrogen, hydroxyl, C₁-C₃₀ linear alkyl, C₁-C₃₀ branchedalkyl, C₁-C₃₀ alkoxy, —CO₂H, —OCH₂CO₂H, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, —PO₃ ²⁻M,—OPO₃ ²⁻M, and mixtures thereof; M is a water soluble cation insufficient amount to satisfy charge balance; x is 0 or 1, each yindependently has the value from 0 to 6, preferably from 0 to 6; each zindependently has the value from 0 to 100, preferably from 0 to about 0,more preferably from 0 to about 3;

i) substituted aryl, and unsubstituted aryl having the formula:

 wherein R¹³ and R¹⁴ are independently selected from the groupconsisting of hydrogen, C₁-C₆ alkyl, C₃-C₆ alkenyl, C₁-C₆ alkoxy, C₁-C₆branched alkoxy, halogen, —CO₂ ⁻M⁺, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, —N(R¹⁵)₂, and—N⁺(R¹⁵)₃X⁻ wherein each R¹⁵ is independently hydrogen or C₁-C₄ alkyl;and mixtures thereof; preferably hydrogen C₁-C₆ alkyl, —CO₂ ⁻M⁺, —OSO₃⁻M⁺, —OSO₃ ⁻M⁺, and mixtures thereof, more preferably R¹³ or R¹⁴ ishydrogen and the other moiety is C₁-C₆ alkyl; wherein M is a watersoluble cation and X is a water soluble anion.

j) substituted alkylenearyl and unsubstituted alkylenearyl having theformula:

 wherein R¹³ and R¹⁴ are as defined above, p is from 1 to about 10.

k) substituted aryloxy and unsubstituted aryloxy having the formula:

 wherein R¹³ and R¹⁴ are as defined above.

l) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl unitsare defined as moieties having the formula:

 wherein R¹³ and R¹⁴ are as defined above, q is from 0 to about 10.

m) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl havingthe formula:

 wherein R¹³ and R¹⁴ are as defined above, w is from about 1 to about10.

n) C₁-C₂₂ linear, C₃-C₂₂ branched thioalkyl, C₁-C₂₂ linear, C₃-C₂₂branched substituted thioalkyl and mixtures thereof;

o) carboxylate units of the formula

 wherein R⁹ is C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, all of which can be substituted with halogen;poly-hydroxyl substituted C₃-C₂₂ alkyl, C₃-C₂₂ glycol; C₁-C₂₂ alkoxy,C₃-C₂₂ branched alkoxy; substituted and unsubstituted aryl,alkylenearyl, aryloxy, oxyalkylenearyl, alkyleneoxyaryl; preferablyC₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, and mixtures thereof;

p) alkyleneamino units having the formula:

 wherein R¹⁰, and R¹¹ are each a C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl,C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, R¹² is hydrogen, C₁-C₂₂ alkyl,C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl andmixtures thereof, the index v is 0 or 1; X is a other water solubleanion, u is from 0 to 22, preferably u is from 3 to about 10. Examplesof water soluble anions include organic species such as fumarate,tartrate, oxalate and the like, inorganic species include chloride,bromide, sulfate, hydrogen sulfate, phosphate and the like;

q) an amino unit of the formula

—NR¹⁷R¹⁸

 wherein R¹⁷ and R¹⁸ are each a C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl,C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof;

r) alkylethyleneoxy units having the formula:

—(A)_(v)—(CH₂)_(y)(CH₂CH₂)_(x)Z

 wherein Z is hydrogen, hydroxyl, —CO₂H, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, C₁-C₆alkoxy, substituted and unsubstituted aryl, substituted andunsubstituted aryloxy; alkyleneamino as defined herein above; ormixtures thereof; A units comprise nitrogen or oxygen, preferablyoxygen; M is a water soluble cation; v is 0 or 1; x is from 0 to 100,preferably from 0 to 20, more preferably from 0 to 5; y is from 0 to 12,preferably from 1 to 4; however, no peroxide —O—O— bonds are containedwithin the photobleaching compounds of the present invention;

s) siloxy and substituted siloxy of the formula —OSiR¹⁹R²⁰R²¹ whereineach R¹⁹, R²⁰, and R²¹ is independently selected from the groupconsisting of C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂C₂₂ alkenyl, C₃-C₂₂branched alkenyl, or mixtures thereof, substituted or unsubstitutedaryl, aryloxy; alkylethyleneoxy units of the formula:

—(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z

 wherein Z is hydrogen, hydroxyl, C₁-C₃₀ alkyl, —CO₂H, —SO₃ ⁻M⁺, —OSO₃⁻M⁺, C₁-C₆ alkoxy; substituted or unsubstituted aryl, and aryloxy;alkyleneamino as defined herein above, and mixtures thereof, preferablyhydrogen or C₁-C₆ alkyl, more preferably methyl; v is 0 or 1; x is from1 to 100, preferably from 0 to about 20, more preferably from 3 to about10; and y is from 0 to 12, preferably from about 0 to about 5.

According to the present invention the preferred axial R units comprisemoieties having the formula

—Y_(i)—K_(j)

and

—Y_(i)—Q_(j)

wherein Y is a linking moiety selected from the group consisting of O,CR²⁵R²⁶, OSiR²⁵R²⁶, OSnR²⁵R²⁶, and mixtures thereof; wherein R²⁵ and R²⁶are hydrogen, C₁-C₄ alkyl, halogen, and mixtures thereof; i is O or 1, jis from 1 to 3;

K is a ligand selected from the group consisting of:

a) C₁-C₃₀ linear alkyl, C₃-C₃₀ branched alkyl, C₂-C₃₀ linear alkenyl,C₃-C₃₀ branched alkenyl, C₆-C₂₀ aryl, C₇-C₂₀ arylalkyl, C₇-C₂₀alkylaryl, and mixtures thereof;

b) an alkylethyleneoxy unit of the formula

—(R²³)_(y)(OR²²)_(x)OZ

 wherein Z is selected from the group consisting of hydrogen, C₁-C₂₀alkyl, C₃-C₂₀ branched alkyl, C₂-C₂₀ linear alkenyl, C₃-C₂₀ branchedalkenyl, C₆-C₂₀ aryl, C₇-C₃₀ arylalkyl, C₆-C₂₀ alkylaryl, and mixturesthereof; R²² is selected from the group consisting of C₁-C₄ linearalkylene, C₃-C₄ branched alkylene, C₃-C₆ hydroxyalkylene, and mixturesthereof; R²³ is selected from the group consisting of C₂-C₂₀ alkylene,C₃-C₂₀ branched alkylene, C₆-C₂₀ arylene, C₇-C₃₀ arylalkylene, C₇-C₃₀alkylarylene, and mixtures thereof; x is from 1 to 100; y is 0 or 1; and

Q is an ionic moiety having the formula:

—R²⁴—W

 wherein R²⁴ is selected from the group consisting of C₃-C₃₀ linearalkylene, C₃-C₃₀ branched alkylene, C₂-C₃₀ linear alkenylene, C₃-C₃₀branched alkenylene, C₆-C₁₆ arylene, and mixtures thereof; W is selectedfrom the group consisting of —CO₂ ⁻M⁺, —SO₃ ⁻M⁺, OSO₃ ⁻M⁺; PO₃ ² ⁻M⁺,—OPO₃ ⁻M⁺, —N⁺(R²⁷)₃X⁻; wherein R²⁷ is independently hydrogen, C₁-C₆alkyl, —(CH₂)_(n)OH, —(CH₂CH₂O)_(n)H, and mixtures thereof; wherein n isfrom 1 to 4; M is a water soluble cation of sufficient charge to provideelectronic neutrality and X is a water soluble anion as defined hereinabove.

Preferred axial R units are alkyl alkyleneoxy units of the formula

—(R²³)_(y)(OR²²)_(x)OZ

wherein Z is selected from the group consisting of hydrogen, C₇-C₂₀linear alkyl, C₃-C₂₀ branched allyl, C₂-C₂₀ linear alkenyl, C₃-C₂₀branched alkenyl, C₆-C₁₀ aryl, C₇-C₂₀ arylalkyl, C₇-C₂₀ alkylaryl, andmixtures thereof; R²² is selected from the group consisting of C₁-C₄linear alkylene, C₃-C₄ branched alkylene, and mixtures thereof; R²³ isselected from the group consisting of C₂-C₆ alkylene, C₃-C₆ branchedalkylene, C₆-C₁₀ arylene, and mixtures thereof; x is from 1 to 50; y is0 or 1.

More preferred axial R units comprise y equal to 0, Z is hydrogen,C₁-C₂₀ alkyl, C₃-C₂₀ branched alkyl, C₆-C₁₀ aryl, and mixtures thereof,most preferred Z is hydrogen or C₆-C₂₀ linear alkyl, C₁₀-C₂₀ branchedalkyl; R²² is C₁-C₄ linear or C₃-C₄ branched alkylene.

Also preferred R units having the formula:

—Y_(i)—Q_(j)

wherein Y is a linking moiety selected from the group consisting of O,CR²⁵R²⁶ OSiR²⁵R²⁶, OSnR²⁵R²⁶, and mixtures thereof; i is 0 or 1, j isfrom 1 to 3; Q is an ionic moiety having the formula:

—R²⁴—W

wherein R²⁴ is selected from the group consisting of C₂-C₂₀ linearalkylene, C₃-C₂₀ branched alkylene, C₂-C₂₀ linear alkenylene, C₃-C₂₀branched alkenylene, C₆-C₁₀ arylene, and mixtures thereof; W is selectedfrom the group consisting of —CO₂ ⁻M⁺, —SO₃ ⁻M⁺, -OSO₃ ⁻M⁺; PO₃ ²⁻M⁺,—OPO₃ ⁻M⁺, —N⁺(R²⁷)₃X⁻; wherein R²⁷ is independently hydrogen, C₁-C₆alkyl, —(CH₂)_(n)H, —(CH₂CH₂O)_(n)H, and mixtures thereof; wherein n isfrom 1 to 4; M is a water soluble cation of sufficient charge to provideelectronic neutrality and X is a water soluble anion as defined hereinabove.

A preferred hydrophilic R has the index i equal to 1; R²⁴ is C₃-C₂₀linear alkylene, C₃-C₂₀ branched alkylene; W is —CO₂ ⁻M⁺, —SO₃ ⁻M⁺,—OSO₃ ⁻M⁺; M is a water soluble cation of sufficient charge to provideelectronic neutrality.

Examples of Y units suitable for use in R units having the formula:

—Y_(i)—K_(j)

have the formula

—O—K¹,

—Sn—K¹,

—OSn—K¹

wherein i is equal to 1 and j is equal to 1. Further examples have theformula

wherein i is equal to 1 and j is equal to 3. The above examples alsoapply to Y units when used with Q ionic moieties.

An example of a preferred photochemical singlet oxygen generatoraccording to the present invention has the following formula:

wherein the photosensitizer unit P comprises an unsubstitutedsilicon(IV) phthalocyanine (R¹-R⁴ of each benzene ring is hydrogen) andthere are two identical D “harvester” units wherein L¹ is an alkyleneoxyunit having the formula:

wherein the indices j and k are equal to 0, x is equal to 2, and i isequal to 15, and the E unit is a-naphthyl. The number of covalent bondsbetween the photosensitizer unit P and the aromatic harvester unit isgreater than 20.

Further examples of photochemical singlet oxygen generators according tothe present invention are the silicon(IV) phthalocyanines having thegeneral formula:

wherein for the first example each D unit has the formula:

wherein L¹ is and alkyleneoxy wherein j and k are equal to 0, x is equalto 2 and i is equal to 2, E is a methyleneanthracene moiety.

A further example comprises two D units having the formula:

wherein L¹ is oxygen, B is silicon, each L² is an alkyleneoxy unitwherein j and k are both equal to 0, x is equal to 2 and i is equal to10, each E unit is a phenanthrene moiety.

The present invention also relates to laundry detergent compositionscomprising:

a) at least about 0.1%, preferably from about 0.1% to about 30%/0, morepreferably from about 1% to about 30%, most preferably from about 5% toabout 20% by weight, of a detersive surfactant, said detersivesurfactant selected from the group consisting of anionic, cationic,zwitterionic, nonionic, and ampholytic surfactants, and mixturesthereof;

b) at least about 0.001 ppm, preferably from about 0.01 to about 10000ppm, more preferably from about 0.1 to about 5000 ppm, most preferablyform about 10 to about 1000 ppm, of a source of singlet oxygen havingthe formula

 wherein P is a photosensitizing group; each D is independently a moietywhich is capable of enhancing the production of singlet oxygen; and R isan axial moiety which mediates the solubility or substantivity of thesinglet oxygen generator as described herein above; and

c) the balance carriers and adjunct ingredients.

It is also an object of the present invention to provide hard surfacecleaning compositions which can be used to clean or disinfect hardsurfaces, said compositions comprising:

a) at least about 0.1%, preferably from about 0.1% to about ³⁰%, morepreferably from about 1% to about 30%, most preferably from about 5% toabout 20% by weight, of a detersive surfactant;

b) at least about 0.001 ppm, preferably from about 0.01 to about 10000ppm, more preferably from about 0.1 to about 5000 ppm, most preferablyform about 10 to about 1000 ppm, of a source of singlet oxygen havingthe formula

 wherein P is a photosensitizing group; each D is independently a moietywhich is capable of enhancing the production of singlet oxygen; and R isan axial moiety which mediates the solubility or substantivity of thesinglet oxygen generator as described herein above; and

c) the balance carriers and adjunct ingredients.

The laundry detergent compositions of the present invention may beliquid, granular or semi-solid, for example a gel, paste, or viscouscream.

The present invention also relates to a method for cleaning a stainedfabric comprising contacting a stained fabric in need of cleaning withan aqueous cleaning solution comprising at least 0.001% of the singletoxygen generator according to the present invention followed by exposingthe surface of the treated fabric to a source of light having a minimalwavelength range from about 300 to about 1200 nanometers.

The present invention also relates to a method for cleaning a hardsurface comprising contacting a hard surface in need of cleaning with anaqueous cleaning composition comprising at least 0.001 % of the singletoxygen generator according to the present invention and exposing thehard surface to a source of light having a minimal wavelength range fromabout 300 to about 1200 nanometers.

Surfactant

The instant singlet oxygen generator containing compositions comprisefrom about 0.001% to about 60% by weight of a surfactant selected fromthe group consisting of anionic, nonionic; ampholytic and zwitterinonicsurface active agents. For liquid systems, surfactant is preferablypresent to the extent of from about 0.1% to 20% by weight of thecomposition. For solid (i.e. granular) and viscous semi-solid (i.e.gelatinous, pastes, etc.) systems, surfactant is preferably present tothe extent of from about 1.5% to 30% by weight of the composition.

Nonlimiting examples of surfactants useful herein typically at levelsfrom about 1% to about 55%, by weight, include the conventional C₁₁-C₁₈alkyl benzene sulfonates (“LAS”) and primary, branched-chain and randomC₁₀-C₂₀ alkyl sulfates (“AS”), the C₁₀-C₁₈ secondary (2,3) alkylsulfates of the formula CH₃(CH₂)_(x)(CHOSO₃ ⁻M⁺) CH₃ and CH₃(CH₂)_(y)(CHOSO₃ ⁻M⁺) CH₂CH₃ where x and (y+1) are integers of at leastabout 7, preferably at least about 9, and M is a water-solubilizingcation, especially sodium, unsaturated sulfates such as oleyl sulfate,the C₁₀-C₁₈ alkyl alkoxy sulfates (“AE_(x)S”; especially EO 1-7 ethoxysulfates), C₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1-5ethoxycarboxylates), the C₁₀-C₁₈ glycerol ethers, the C₁₀-C₁₈ alkylpolyglycosides and their corresponding sulfated polyglycosides, andC₁₂-C₁₈ alpha-sulfonated fatty acid esters. If desired, the conventionalnonionic and amphoteric surfactants such as the C₁₂-C₁₈ alkylethoxylates (“AE”) including the so-called narrow peaked alkylethoxylates and C₆-C₁₂ alkyl phenol alkoxylates (especially ethoxylatesand mixed ethoxy/propoxy), C₁₂-C₁₈ betaines and sulfobetaines(“sultaines”), C₁₀-C₁₈ amine oxides, and the like, can also be includedin the overall compositions. The C₁₀-C₁₈ N-alkyl polyhydroxy fatty acidamides can also be used. Typical examples include the C₁₂-C₁₈N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactantsinclude the N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈N—(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂-C₁₈glucamides can be used for low sudsing. C₁₀-C₂₀ conventional soaps mayalso be used. If high sudsing is desired, the branched-chain C₁₀-C₁₆soaps may be used. Mixtures of anionic and nonionic surfactants areespecially useful. Other conventional useful surfactants are describedfurther herein and are listed in standard texts.

Anionic surfactants can be broadly described as the water-soluble salts,particularly the alkali metal salts, of organic sulfuric reactionproducts having in their molecular structure an alkyl radical containingfrom about 8 to about 22 carbon atoms and a radical selected from thegroup consisting of sulfonic acid and sulfuric acid ester radicals.(Included in the term alkyl is the alkyl portion of higher acylradicals.) Important examples of the anionic synthetic detergents whichcan form the surfactant component of the compositions of the presentinvention are the sodium or potassium alkyl sulfates, especially thoseobtained by sulfating the higher alcohols (C8-18 carbon atoms) producedby reducing the glycerides of tallow or coconut oil; sodium or potassiumalkyl benzene sulfonates, in which the alkyl group contains from about 9to about 15 carbon atoms, (the alkyl radical can be a straight orbranched aliphatic chain); sodium alkyl glyceryl ether sulfonates,especially those ethers of the higher alcohols derived from tallow andcoconut oil; sodium coconut oil fatty acid monoglyceride sulfates andsulfonates; sodium or potassium salts of sulfuric acid ester of thereaction product of one mole of a higher fatty alcohol (e.g. tallow orcoconut alcohols) and about 1 to about 10 moles of ethylene oxide;sodium or potassium salts of alkyl phenol ethylene oxide ether sulfateswith about 1 to about 10 units of ethylene oxide per molecule and inwhich the alkyl radicals contain from 8 to 12 carbon atoms; the reactionproducts of fatty acids are derived from coconut oil sodium or potassiumsalts of tatty acid amides of a methyl tauride in which the fatty acids,for example, are derived from coconut oil and sodium or potassiumbeta-acetoxy- or beta-acetamido-alkanesulfonates where the alkane hasfrom 8 to 22 carbon atoms.

Additionally, secondary alkyl sulfates may be used by the formulatorexclusively or in conjunction with other surfactant materials and thefollowing identifies and illustrates the differences between sulfatedsurfactants and otherwise conventional alkyl sulfate surfactants.Non-limiting examples of such ingredients are as follows.

Conventional primary alkyl sulfates, such as those illustrated above,have the general formula ROSO3—M+ wherein R is typically a linear C8-22hydrocarbyl group and M is a water solublizing cation. Branched chainprimary alkyl sulfate surfactants (i.e., branched-chain “PAS”) having8-20 carbon atoms are also know; see, for example, Eur. Pat. Appl.439,316, Smith et al., filed Jan. 21, 1991.

Conventional secondary alkyl sulfate surfactants are those materialswhich have the sulfate moiety distributed randomly along the hydrocarbyl“backbone” of the molecule. Such materials may be depicted by thestructure

CH₃(CH₂)_(n)(CHOSO₃ ⁻M⁺)(CH₂)_(m)CH₃

wherein m and n are integers of 2 of greater and the sum of m+n istypically about 9 to 17, and M is a water-solublizing cation.

The aforementioned secondary alkyl sulfates are those prepared by theaddition of H₂SO₄ to olefins. A typical synthesis using alpha olefinsand sulfuric acid is disclosed in U.S. Pat. No. 3,234,258, Morris,issued Feb. 8, 1966 or in U.S. Pat. No. 5,075,041, Lutz, issued Dec. 24,1991. The synthesis conducted in solvents which afford the secondary(2,3) alkyl sulfates on cooling, yields products which, when purified toremove the unreacted materials, randomly sulfated materials, unsulfatedby-products such as C10 and higher alcohols, secondary olefinsulfonates, and the like, are typically 90+% pure mixture of 2- and3-sulfated materials (some sodium sulfate may be present) and are white,non tacky, apparently crystalline, solids. Some 2,3-disulfates may alsobe present, but generally comprise no more than 5% of the mixture ofsecondary (2,3) alkyl mono-sulfates. Such materials are available asunder the name “DAN”, e.g., “DAN 200” from Shell Oil Company.

Adjunct Materials

The following are non-limiting examples of adjunct ingredients suitablefor use in either laundry or hard surface cleaning or disinfectingcompositions according to the present invention.

Chelating Agents

The photo disinfectant compositions herein may also optionally containone or more iron and/or manganese chelating agents. Such chelatingagents can be selected from the group consisting of amino carboxylates,amino phosphonates, polyfunctionally-substituted aromatic chelatingagents and mixtures therein, all as hereinafter defined. Withoutintending to be bound by theory, it is believed that certain chelatingagents will interact with photodisinfectants of the present invention toincrease their absorbency in the visible light spectrum. This is aprocess that is due to the ability of chelating agents to help effectthe “substantiveness” of the compounds of the present invention.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate (“EDDS”), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

If utilized, these chelating agents will generally comprise from about0.1% to about 10% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Inert Salts

The inert salts (filler salts) used in the compositions of the presentinvention can be any water-soluble inorganic or organic salt or mixturesof such salts which do not destabilize any surfactant present. For thepurposed of the present invention, “water-soluble” means having asolubility in water of at least I gram per 100 grams of water at 20° C.Examples of suitable salts include various alkali metal and/or alkaliearth metal sulfate, chlorides, borates, bromides, fluorides,phosphates, carbonates, bicarbonates, citrates, acetates, lactates, etc.

Specific examples of suitable salts include sodium sulfate, sodiumchloride, potassium chloride, sodium carbonate, potassium sulfate,lithium chloride, lithium sulfate, tripotassium phosphate, sodiumborate, potassium bromide, potassium fluoride, sodium bicarbonate,magnesium sulfate, magnesium chloride, sodium citrate, sodium acetate,magnesium lactate, sodium fluoride. The preferred salts are inorganicsalts preferably the alkali metal sulfates and chlorides. Particularlypreferred salts, because of their low cost are sodium sulfate and sodiumchloride. The salts are present in the compositions at levels of from 0%to 40%. preferably 10% to 20%.

EXAMPLE 1 Preparation of silicon phthalocyanine dichloride

To a mixture of 1,3diiminoisoindoline (0.333 gm, 2.3 mmole) andanhydrous quinoline (15 mL) under argon blanketing is added silicontetrachloride (1.1 g, 6.5 mmole). The mixture is lowered into an oilbath at 60° C. for 0.5 hr, heated to reflux over 0.5 hr, stirred atreflux for an additional 0.5 hr and cooled over 1 hr. To this solutionis added methanol (10 mL) and the resultant mixture is allowed to standat room temperature for 24 hr. The blue solid which forms upon standingis filtered off, rinsed twice with 10 mL portions of methanol, driedunder vacuum at 120° C. and used without further purification.

The above procedure is suitable for use in preparing siliconnaphthalocyanine dichloride using 1,3-diiminobenz-[f]-isoindoline.

EXAMPLE 2 Preparation of 1:3 silicon(VI)phthalo/naphthalocyaninedichloride

To a mixture of 1,3-diiminoisoindoline (0.333 gm, 2.3 mmole),1,3-diiminobenz[f]-isoindoline (1.35 gm, 6.9 mmole) and anhydrousquinoline (15 mL) under argon blanketing is added silicon tetrachloride(2.21 g, 12.9 mmole). The mixture is lowered into an oil bath at 60° C.for 0.5 hr, heated to reflux over 0.5 hr, stirred at reflux 0.5 hr andcooled over 1 hr. To this solution is added methanol (10 mL) and theresultant mixture is allowed stand at room temperature for 24 hr. Thegreen solid which forms is removed by filtration, rinsed twice with 10mL portions of methanol, dried under vacuum at 120° C. and used withoutfurther purification.

EXAMPLE 3 Preparation of silicon phthalocyanine dihydroxide

Silicon (IV) phthalocyanine dichloride (2 gm, 3.3 mmole) is added to arefluxing solution of sodium methoxide (0.8 g, 14.8 mmole) in 95% wetethanol (15 mL). The reaction mixture is refluxed 4 hr then cooled toroom temperature. The resulting product is collected by filtration,rinsed with water and used without subsequent purification.

The above procedure is suitable for use in preparing siliconnaphthalocyanine dihydroxide, and 1:3 silicon (IV)phthalo/naphthalocyanine dihydroxide.

EXAMPLE 4 Preparation of dilithium naphthalocyanine

To a refluxing solution of 2,3-dicyanonaphthalene (10 gm, 56.1 mmole) inanhydrous 1-butanol (300 mL) is added lithium shot (1.56 gm, 224.5mmole). The solution is refluxed 6 hr under a blanket of argon afterwhich time the solution is cooled, diluted with absolute methanol (500mL) and allowed to stand at 0° C. for 18 hr. The green solid whichresults is collected by filtration, dried under vacuum at 80° C. andused without further purification.

The above procedure is suitable for use in preparing1,4,8,11,15,18,22,25-octabutoxy-29,31-dilithium phthalocyanine from3,6-dibutoxyphthalonitrile;2,3,9,10,16,17,23,24-octachloro29-31-dilithium phthalocyanine from4,5-dichlorophthalonitrile; and tetrabutoxy-29,31-dilithiumphthalocyanine from 3-butoxyphthalonitrile wherein there is a mixture ofisomers.

EXAMPLE 5 Preparation of naphthalocyanine

To a solution of dilithium naphthalocyanine (2 gm, 2.75 mmole) inN,N-Dimethylformamide (200 mL) is added 1N hydrochloric acid (10 mL).The solution is stirred at room temperature for 1 hr. To this solutionis added distilled water (200 mL) over approximately 0.5 hr. The greensolid which forms is collected by filtration, dried under vacuum at 100°C. and used without further purification.

The above procedure is suitable for use in preparing1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine;2,3,9,10,16,17,23,24-octachloro-29H,31H-phthalocyanine; andtetrabutoxy-29H,31H-phthalocyanine.

EXAMPLE 6 Ethoxylation of 1-naphthaleneethanol to an average of 15ethyleneoxy units.

To a dried 250 mL 3 neck round bottom flask, fitted with a gas inlettube, overhead mechanical stirrer, and a Y-tube which is equipped with athermometer and a gas outlet tube is charged 1-naphthaleneethanol (20gm, 116.3 mmole). Under nitrogen blanketing sodium metal (0.11 gm, 5mmole) is added and the resulting mixture heated to from about 120 toabout 140° C. With vigorous stirring, ethylene oxide gas (80 gm, 1.82 amole) is added while maintaining the within the range of from 120 toabout 140° C. After addition of ethylene oxide is complete, nitrogen isswept through the apparatus for 20-30 minutes as the reaction solutionis allowed to cool. The yellow/brown liquid product which results isused without further purification.

The above procedure is suitable for use to ethoxylate 1-anthracene to anaverage degree of ethoxylation of 15 (E15).

EXAMPLE 7 Preparation of silicon phthalocyanine-di-[pentadecyl(ethyleneglycol) mono-1-ethylnaphthalene ether]

Silicon phthalocyanine dihydroxide (0.25 gm, 0.44 mmole), anhydrous1-naphthalenepentadecylethylene glycol (10 gm, 17.4 mmole) and xylenes(175 mL) are combined and heated to reflux over 1.5 hr. The solution iscontinued at reflux for 2 hr. while water is removed by azeotropicdistillation. The resulting green liquid is used without furtherpurification.

The above procedure is suitable for use in preparing siliconnaphthalocyanine-di-[pentadecyl(ethylene glycol) mono-1-ethylnaphthaleneether]; silicon naphthalocyanine-di-[pentadecyl(ethyleneglycol)mono-1-methylanthracene ether); and 1:3 Silicon(VI)phthalo/naphthalocyanine-di-[pentadecyl(ethylene glycol)mono-1-ethylnaphthalene ether]. The cleaning compositions provided inaccordance with this invention may be in the form of granules, liquids,bars, and the like, and typically are formulated to provide an in-use pHin the range of 9 to 11, however in the case of non-aqueous or lowaqueous compositions the pH ranges may vary outside this range. Variouscarriers such as sodium sulfate, water, water-ethanol, BPP, MPP, EPP,PPP, sodium carbonate, and the like, may be used routinely to formulatethe finished products. Granules may be produced by spray-drying or byagglomeration, using known techniques, to provide products in thedensity range of 350-950 g/l. Bars may be formulated using conventionalextrusion techniques. The compositions may also contain conventionalperfumes, bactericides, hydrotropes and the like. In the case ofnon-aqueous or low aqueous compositions, the cleaning compositions maybe applied to an article which is used to deliver the compositions ofthe present invention to a fabric or to a hard surface. Non-limitingexamples of compositions according to this invention are as follows:

weight % Ingredients 21 22 23 24 Sodium LAS 15 30 20 25 NEODOL 1 1 1 1Alkyl Dimethyl 0.5 1 0.5 0.7 Ammonium Chloride Sodium Tripolyphosphate15 35 22 28 Sodium Carbonate 10 10 15 15 SOKALAN 2 2 2 2 CarboxymethylCellulose 1 1 1 1 Tinopal CBS-X 0.1 0.1 0.1 0.1 Soil Release Agent¹ 0.20.2 0.3 0.3 Savinase 6.0T 0.3 0.6 0.5 0.6 BAN 300T 0.2 0.5 0.5 0.6Lipolase 100T 0.1 0.2 0.2 0.3 CAREZYME 5T 0.1 0.2 0.2 0.3 SodiumPerborate — — 3.0 5.0 NOBS — — 2.0 3.0 Photobleach² (ppm) 0.005 0.010.008 0.01 Moisture + SodiumSulfate + Balance Balance Balance BalancePerfume + Miscellaneous ¹Soil Release Agent according to U.S. Pat. No.5,415,807 Gosselink et al., issued May 16, 1995. ²Photobleach accordingto Example 7.

What is claimed is:
 1. A singlet oxygen generator having the formula:

wherein P is a photosensitizer unit having the formula:

or the formula:

wherein M is a photoactive metal or non-metal having a valence greaterthan or equal to 3 which is selected from the group consisting ofsilicon, phosphorous, palladium, platinum, lead, germanium, tin, andmixtures thereof; rings A, B, C, and D are aromatic rings, wherein eachof said rings A, B, C, and D are each independently: i) a benzene ringunit having the formula:

ii) a 2,3-naphthylene ring unit having the formula:

iii) a 1,2-naphthylene ring unit having the formula:

iv) an anthracene ring unit having the formula:

v) an phenanthrene ring unit having the formula:

 wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ unit is independentlyselected from the group consisting of: a) hydrogen; b) halogen; c)hydroxy; d) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂branched alkenyl, or mixtures thereof; e) halogen substituted C₁-C₂₂alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl,or mixtures thereof; f) polyhydroxyl substituted C₃-C₂₂ alkyl; g) C₁-C₂₂alkoxy; h) branched alkoxy having the formula:

 wherein Z is hydrogen, hydroxyl, C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, —CO₂H,—OCH₂CO₂H, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, —PO₃ ²⁻M, OPO₃ ²⁻M, or mixtures thereof;M is a water soluble cation in sufficient amount to satisfy chargebalance;  x is 0 or 1, each y independently has the value from 0 to 6,each z independently has the value from 0 to 100; i) substituted aryl,unsubstituted aryl, or mixtures thereof; j) substituted alkylenearyl,unsubstituted alkylenearyl, or mixtures thereof; k) substituted aryloxy,unsubstituted aryloxy, or mixtures thereof; l) substitutedoxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof; m)substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixturesthereof; n) C₁-C₂₂ thioalkyl, C₃-C₂₂ branched thioalkyl, or mixturesthereof; o) an ester of the formula —CO₂R⁹ wherein R⁹ is i) C₁-C₂₂alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl,or mixtures thereof; ii) halogen substituted C₁-C₂₂ alkyl, C₃-C₂₂branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixturesthereof; iii) polyhydroxyl substituted C₃-C₂₂ alkylene; iv) C₃-C₂₂glycol; v) C₁-C₂₂ alkoxy; vi) C₃-C₂₂ branched alkoxy; vii) substitutedaryl, unsubstituted aryl, or mixtures thereof; viii) substitutedalkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; ix)substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x)substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixturesthereof; xi) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl,or mixtures thereof; p) an alkyleneamino unit of the formula:

 wherein R¹⁰and R¹¹ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof;  R¹² is: i)hydrogen; ii) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof; A is nitrogen or oxygen; Xis chlorine, bromine, iodine, or other water soluble anion, v is 0 or 1,u is from 0 to 22; q) an amino unit of the formula: —NR¹⁷R¹⁸  whereinR¹⁷ and R¹⁸ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof; r) an alkylethyleneoxyunit of the formula: —(A)_(v)(CH₂)_(y)(OCH₂CH₂)_(x)Z  wherein Z is: i)hydrogen; ii) hydroxyl; iii) —CO₂H; iv) —SO₃ ⁻M⁺; v) —OSO₃ ⁻M⁺; vi)C₁-C₆ alkoxy; vii) substituted aryl, unsubstituted aryl, or mixturesthereof; viii) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; ix) alkyleneamino; or mixtures thereof; A is nitrogen oroxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, yis from 0 to 12; s) substituted siloxy of the formula: —OSiR¹⁹R²⁰R²¹ wherein each R¹⁹, R²⁰, and R²¹ is independently i) C₁-C₂₂ alkyl, C₃-C₂₂branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixturesthereof; ii) substituted aryl, unsubstituted aryl, or mixtures thereof;iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;iv) an alkylethyleneoxy unit of the formula:—(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z wherein Z is: a) hydrogen; b) hydroxyl;c) —CO₂H; d) —SO₃ ⁻M⁺; e) —OSO₃ ⁻M⁺; f) C₁-C₆ alkoxy; g) substitutedaryl, unsubstituted aryl, or mixtures thereof; h) substituted aryloxy,unsubstituted aryloxy, or mixtures thereof; i) alkyleneamino; ormixtures thereof;  A is nitrogen or oxygen, M is a water soluble cation,v is 0 or 1, x is from 0 to 100, y is from 0 to 12;  and mixturesthereof; R is an axial moiety which mediates the solubility orsubstantivity of the singlet oxygen generator wherein R is selectedfrom: a) hydrogen; b) halogen; c) hydroxy; d) C₁-C₂₂ alkyl, C₃-C₂₂branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixturesthereof; e) halogen substituted C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl,C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof; f)polyhydroxyl substituted C₃-C₂₂ alkyl; g) C₁-C₂₂ alkoxy; h) branchedalkoxy having the formula:

 wherein Z is hydrogen, hydroxyl, C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, —CO₂H,—OCH₂CO₂H, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, PO₃ ²⁻M, —OPO₃ ²⁻M, or mixtures thereof;M is a water soluble cation in sufficient amount to satisfy chargebalance; x is 0 or 1, each y independently has the value from 0 to 6,each z independently has the value from 0 to 100; i) substituted aryl,unsubstituted aryl, or mixtures thereof; j) substituted alkylenearyl,unsubstituted alkylenearyl, or mixtures thereof; k) substituted aryloxy,unsubstituted aryloxy, or mixtures thereof; l) substitutedoxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof; m)substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixturesthereof; n) C₁-C₂₂ thioalkyl, C₃-C₂₂ branched thioalkyl, or mixturesthereof; o) a carboxylate of the formula:

 wherein R⁹ is: i) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof; ii) halogen substitutedC₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branchedalkenyl, or mixtures thereof; iii) polyhydroxyl substituted C₃-C₂₂alkylene; iv) C₃-C₂₂ glycol; v) C₁-C₂₂ alkoxy; vi) C₃-C₂₂ branchedalkoxy; vii) substituted aryl, unsubstituted aryl, or mixtures thereof;viii) substituted alkylenearyl, unsubstituted alkylenearyl, or mixturesthereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; x) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl,or mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstitutedalkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of theformula:

 wherein R¹⁰ and R¹¹ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof;  R¹² is: i)hydrogen; ii) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof;  A is nitrogen or oxygen;X is chlorine, bromine, iodine, or other water soluble anion, v is 0 or1, u is from 0 to 22; q) an amino unit of the formula: —NR¹⁷R¹⁸  whereinR¹⁷ and R¹⁸ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof; r) an alkylethyleneoxyunit of the formula: —(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z  wherein Z is: i)hydrogen; ii) hydroxyl; iii) —CO₂H; iv) —SO₃ ⁻M⁺; v) —OSO₃ ⁻M⁺; vi)C₁-C₆ alkoxy; vii) substituted aryl, unsubstituted aryl, or mixturesthereof; viii) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; ix) alkyleneamino; or mixtures thereof;  A is nitrogen oroxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, yis from 0 to 12; s) substituted siloxy of the formula: —OSiR¹⁹R²⁰R²¹ wherein each R¹⁹, R²⁰, and R²¹ is independently i) C₁-C₂₂ alkyl, C₃-C₂₂branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixturesthereof; ii) substituted aryl, unsubstituted aryl, or mixtures thereof;iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;iv) an alkylethyleneoxy unit of the formula:—(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z;  wherein Z is: a) hydrogen; b)hydroxyl; c) —CO₂H; d) —SO₃ ⁻M⁺; e) —OSO₃ ⁻M⁺; f) C₁-C₆ alkoxy; g)substituted aryl, unsubstituted aryl, or mixtures thereof; h)substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; i)alkyleneamino; or mixtures thereof;  A is nitrogen or oxygen, M is awater soluble cation, v is 0 or 1, x is from 0 to 100, y is from 0 to12; and mixtures thereof; and D is a unit which increases the efficiencyof singlet oxygen production, said unit having the formula —L¹—E or—L¹—B—[L²—E]_(m) wherein E is an aromatic unit, provided said E aromaticunit: a) absorbs ultra violet radiation at a wavelength of from about200 nm to about 400 nm; b) has an extinction coefficient of at leastabout 100; and c) has a fluorescence spectrum which overlaps theabsorption band of said photosensitizer unit; B is a branching unit; andL¹ and L² are linking units, provided said linking units when takentogether with said B unit comprise a total of at least 20 continuouscovalent bonds from said P unit to said E units; m is from 2 to
 4. 2. Acompound according to claim 1 wherein L¹ and L² are independentlyselected from the group consisting of oxygen, linear or branchedalkylene, linear or branched alkenylene; linear or branched alkyleneoxy,substituted or unsubstituted arylene, substituted or unsubstitutedalkylenearylene, substituted or unsubstituted aryleneoxy, substituted orunsubstituted oxyalkylenearylene, substituted or unsubstitutedalkyleneoxyarylene, and mixtures thereof.
 3. A compound according toclaim 1 wherein the branching unit B has the formula:

wherein B is selected from the group consisting of boron, aluminum,nitrogen, phosphorous, carbon, silicon, tin, germanium, and mixturesthereof.
 4. A compound according to claim 1 wherein the E unit has anextinction coefficient of at least
 1000. 5. A compound according toclaim 4 wherein the E unit has an extinction coefficient of at least10,000.
 6. A laundry detergent composition comprising: a) from about0.1%, to about 20% by weight, of a detersive surfactant; b) from about0.001 ppm to about 1000 ppm, of a singlet oxygen generator as set forthin claim 1; and c) the balance carriers and adjunct ingredients.
 7. Acomposition according to claim 6 wherein the detersive surfactant isselected from the group consisting of anionic, cationic, nonionic,zwitterionic, ampholytic surfactants, and mixtures thereof.
 8. Acomposition according to claim 6 wherein the adjunct ingredients aremembers selected from the group consisting of buffers, builders,chelants, filler salts, soil release agents, dispersants, enzymes,enzyme boosters, perfumes, thickeners, abrasives, solvents, clays, andmixtures thereof.
 9. A composition according to claim 6 wherein the Eunit has an extinction coefficient of at least
 1000. 10. A compositionaccording to claim 9 wherein the E unit has an extinction coefficient ofat least 10,000.
 11. A method for cleaning a stained fabric comprisingcontacting a stained fabric in need of cleaning with an aqueous cleaningsolution comprising at least 0.01% of the singlet oxygen generatoraccording to claim 1 followed by exposing the surface of the treatedfabric to a source of light having a minimal wavelength range from about300 to about 1200 nanometers.
 12. A method for cleaning a hard surfacecomprising contacting a hard surface in need of cleaning with an aqueouscleaning composition comprising at least 0.001 ppm of the singlet oxygengenerator according to claim 1 and exposing the hard surface to a sourceof light having a minimal wavelength range from about 300 to about 1200nanometers.
 13. A method for generating oxygen comprising exposing asinglet oxygen generator according to claim 1 to a source of lighthaving a minimal wavelength range from about 300 to about 1200nanometers.
 14. A singlet oxygen generator having the formula:

wherein P is a photosensitizer unit having the formula:

or the formula:

wherein M is a photoactive metal or non-metal having a valence greaterthan or equal to 3 which is selected from the group consisting ofsilicon, phosphorous, palladium, platinum, lead, germanium, tin, andmixtures thereof; rings A, B, C, and D are aromatic rings, wherein eachof said rings A, B, C, and D are each independently: i) a benzene ringunit having the formula:

ii) a 2,3-naphthylene ring unit having the formula:

iii) a 1,2-naphthylene ring unit having the formula:

iv) an anthracene ring unit having the formula:

v) an phenanthrene ring unit having the formula:

 wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ unit is independentlyselected from the group consisting of: a) hydrogen; b) halogen; c)hydroxy; d) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂branched alkenyl, or mixtures thereof; e) halogen substituted C₁-C₂₂alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl,or mixtures thereof; f) polyhydroxyl substituted C₃-C₂₂ alkyl; g) C₁-C₂₂alkoxy; h) branched alkoxy having the formula:

 wherein Z is hydrogen, hydroxyl, C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, —CO₂H,—OCH₂CO₂H, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, —PO₃ ²⁻M, —OPO₃ ²⁻M, or mixturesthereof; M is a water soluble cation in sufficient amount to satisfycharge balance;  x is 0 or 1, each y independently has the value from 0to 6, each z independently has the value from 0 to 100; i) substitutedaryl, unsubstituted aryl, or mixtures thereof; j) substitutedalkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; k)substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; l)substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixturesthereof; m) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl,or mixtures thereof; n) C₁-C₂₂ thioalkyl, C₃-C₂₂ branched thioalkyl, ormixtures thereof; o) an ester of the formula —CO₂R⁹ wherein R⁹ is i)C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branchedalkenyl, or mixtures thereof; ii) halogen substituted C₁-C₂₂ alkyl,C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, ormixtures thereof; iii) polyhydroxyl substituted C₃-C₂₂ alkylene; iv)C₃-C₂₂ glycol; v) C₁-C₂₂ alkoxy; vi) C₃-C₂₂ branched alkoxy; vii)substituted aryl, unsubstituted aryl, or mixtures thereof; viii)substituted alkylenearyl, unsubstituted alkylenearyl, or mixturesthereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; x) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl,or mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstitutedalkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of theformula:

 wherein R¹⁰ and R¹¹ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof;  R¹² is: i)hydrogen; ii) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof;  A is nitrogen or oxygen;X is chlorine, bromine, iodine, or other water soluble anion, v is 0 or1, u is from 0 to 22; q) an amino unit of the formula: —NR¹⁷R¹⁸  whereinR¹⁷ and R¹⁸ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof; r) an alkylethyleneoxyunit of the formula: —(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z  wherein Z is: i)hydrogen; ii) hydroxyl; iii) —CO₂H; iv) —SO₃ ⁻M⁺; v) —OSO₃ ⁻M⁺; vi)C₁-C₆ alkoxy; vii) substituted aryl, unsubstituted aryl, or mixturesthereof; viii) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; ix) alkyleneamino; or mixtures thereof;  A is nitrogen oroxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, yis from 0 to 12; s) substituted siloxy of the formula: —OSiR¹⁹R²⁰R²¹ wherein each R¹⁹, R²⁰, and R²¹ is independently i) C₁-C₂₂ alkyl, C₃-C₂₂branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixturesthereof; ii) substituted aryl, unsubstituted aryl, or mixtures thereof;iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;iv) an alkylethyleneoxy unit of the formula:—(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z;  wherein Z is: a) hydrogen; b)hydroxyl; c) —CO₂H; d) —SO₃ ⁻M⁺; e) —OSO₃ ⁻M⁺; f) C₁-C₆ alkoxy; g)substituted aryl, unsubstituted aryl, or mixtures thereof; h)substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; i)alkyleneamino; or mixtures thereof;  A is nitrogen or oxygen, M is awater soluble cation, v is 0 or 1, x is from 0 to 100, y is from 0 to12;  and mixtures thereof; R is an axial moiety which mediates thesolubility or substantivity of the singlet oxygen generator wherein R isselected from: a) hydrogen; b) halogen; c) hydroxy; d) C₁-C₂₂ alkyl,C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, ormixtures thereof; e) halogen substituted C₁-C₂₂ alkyl, C₃-C₂₂ branchedalkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof; f)polyhydroxyl substituted C₃-C₂₂ alkyl; g) C₁-C₂₂ alkoxy; h) branchedalkoxy having the formula:

 wherein Z is hydrogen, hydroxyl, C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, —CO₂H,—OCH₂CO₂H, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, —PO₃ ²⁻M, —OPO₃ ²⁻M, or mixturesthereof; M is a water soluble cation in sufficient amount to satisfycharge balance; x is 0 or 1, each y independently has the value from 0to 6, each z independently has the value from 0 to 100; i) substitutedaryl, unsubstituted aryl, or mixtures thereof; j) substitutedalkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; k)substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; l)substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixturesthereof; m) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl,or mixtures thereof; n) C₁-C₂₂ thioalkyl, C₃-C₂₂ branched thioalkyl, ormixtures thereof; o) a carboxylate of the formula:

 wherein R⁹ is: i) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof; ii) halogen substitutedC₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branchedalkenyl, or mixtures thereof; iii) polyhydroxyl substituted C₃-C₂₂alkylene; iv) C₃-C₂₂ glycol; v) C₁-C₂₂ alkoxy; vi) C₃-C₂₂ branchedalkoxy; vii) substituted aryl, unsubstituted aryl, or mixtures thereof;viii) substituted alkylenearyl, unsubstituted alkylenearyl, or mixturesthereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; x) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl,or mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstitutedalkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of theformula:

 wherein R¹⁰ and R¹¹ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof;  R¹² is: i)hydrogen; ii) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof;  A is nitrogen or oxygen;X is chlorine, bromine, iodine, or other water soluble anion, v is 0 or1, u is from 0 to 22; q) an amino unit of the formula: —NR¹⁷R¹⁸  whereinR¹⁷ and R¹⁸ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof; r) an alkylethyleneoxyunit of the formula: —(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z  wherein Z is: i)hydrogen; ii) hydroxyl; iii) —CO₂H; iv) —SO₃ ⁻M⁺; v) —OSO₃ ⁻M⁺; vi)C₁-C₆ alkoxy; vii) substituted aryl, unsubstituted aryl, or mixturesthereof; viii) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; ix) alkyleneamino; or mixtures thereof;  A is nitrogen oroxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, yis from 0 to 12; s) substituted siloxy of the formula: —OSiR¹⁹R²⁰R²¹ wherein each R¹⁹, R²⁰, and R²¹ is independently i) C₁-C₂₂ alkyl C₃-C₂₂branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixturesthereof; ii) substituted aryl, unsubstituted aryl, or mixtures thereof;iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;iv) an alkylethyleneoxy unit of the formula:—(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z;  wherein Z is: a) hydrogen; b)hydroxyl; c) —CO₂H; d) —SO₃ ⁻M⁺; e) —OSO₃ ⁻M⁺; f) C₁-C₆ alkoxy; g)substituted aryl, unsubstituted aryl, or mixtures thereof; h)substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; i)alkyleneamino; or mixtures thereof;  A is nitrogen or oxygen, M is awater soluble cation, v is 0 or 1, x is from 0 to 100, y is from 0 to12; and mixtures thereof; and D is a unit which increases the efficiencyof singlet oxygen production, said unit having the formula —L¹—E  or—L¹—B—[L²—E]_(m) wherein E is an aromatic unit having six carbon atoms,provided said E aromatic unit: a) absorbs ultra violet radiation at awavelength of from about 200 nm to about 400 nm; b) has an extinctioncoefficient of at least about 100; and c) has a fluorescence spectrumwhich overlaps the absorption band of said photosensitizer unit; B is abranching unit; and L¹ and L² are linking units, provided said linkingunits when taken together with said B unit comprise a total of at least20 continuous covalent bonds from said P unit to said E units; m is from2 to
 4. 15. A singlet oxygen generator having the formula:

wherein P is a photosensitizer unit having the formula:

or the formula:

wherein M is a photoactive metal or non-metal having a valence greaterthan or equal to 3 which is selected from the group consisting ofsilicon, phosphorous, palladium, platinum, lead, germanium, tin, andmixtures thereof, rings A, B, C, and D are aromatic rings, wherein eachof said rings A, B, C, and D are each independently: i) a benzene ringunit having the formula:

ii) a 2,3-naphthylene ring unit having the formula:

iii) a 1,2-naphthylene ring unit having the formula:

iv) an anthracene ring unit having the formula:

v) an phenanthrene ring unit having the formula:

 wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸ unit is independentlyselected from the group consisting of: a) hydrogen; b) halogen; c)hydroxy; d) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂branched alkenyl, or mixtures thereof; e) halogen substituted C₁-C₂₂alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl,or mixtures thereof; f) polyhydroxyl substituted C₃-C₂₂ alkyl; g) C₁-C₂₂alkoxy; h) branched alkoxy having the formula:

 wherein Z is hydrogen, hydroxyl, C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, —CO₂H,—OCH₂CO₂H, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, —PO₃ ²⁻M, —OPO₃ ²⁻M, or mixturesthereof; M is a water soluble cation in sufficient amount to satisfycharge balance;  x is 0 or 1, each y independently has the value from 0to 6, each z independently has the value from 0 to 100; i) substitutedaryl, unsubstituted aryl, or mixtures thereof; j) substitutedalkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; k)substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; l)substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixturesthereof; m) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl,or mixtures thereof; n) an ester of the formula —CO₂R⁹ wherein R⁹ is i)C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branchedalkenyl, or mixtures thereof; ii) halogen substituted C₁-C₂₂ alkyl,C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, ormixtures thereof; iii) polyhydroxyl substituted C₃-C₂₂ alkylene; iv)C₃-C₂₂ glycol; v) C₁-C₂₂ alkoxy; vi) C₃-C₂₂ branched alkoxy; vii)substituted aryl, unsubstituted aryl, or mixtures thereof; viii)substituted alkylenearyl, unsubstituted alkylenearyl, or mixturesthereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; x) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl,or mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstitutedalkyleneoxyaryl, or mixtures thereof; o) an alkyleneamino unit of theformula:

 wherein R¹⁰ and R¹¹ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof;  R¹² is: i)hydrogen; ii) C₁C₂₂ alkyl , C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof;  A is nitrogen or oxygen;X is chlorine, bromine, iodine, or other water soluble anion, v is 0 or1, u is from 0 to 22; p) an amino unit of the formula: —NR¹⁷R¹⁸  whereinR¹⁷ and R¹⁸ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof; q) an alkylethyleneoxyunit of the formula: —(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z  wherein Z is: i)hydrogen; ii) hydroxyl; iii) —CO₂H; iv) —SO₃ ⁻M⁺; v) —OSO₃ ⁻M⁺; vi)C₁-C₆ alkoxy; vii) substituted aryl, unsubstituted aryl, or mixturesthereof; viii) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; ix) alkyleneamino; or mixtures thereof;  A is nitrogen oroxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, yis from 0 to 12; r) substituted siloxy of the formula: —OSiR¹⁹R²⁰R²¹ wherein each R¹⁹, R²⁰, and R²¹ is independently i) C₁-C₂₂ alkyl, C₃-C₂₂branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixturesthereof; ii) substituted aryl, unsubstituted aryl, or mixtures thereof;iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;iv) an alkylethyleneoxy unit of the formula:—(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z;  wherein Z is: a) hydrogen; b)hydroxyl; c) —CO₂H; d) —SO₃ ⁻M⁺; e) —OSO₃ ⁻M⁺; f) C₁-C₆ alkoxy; g)substituted aryl, unsubstituted aryl, or mixtures thereof; h)substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; i)alkyleneamino; or mixtures thereof;  A is nitrogen or oxygen, M is awater soluble cation, v is 0 or 1, x is from 0 to 100, y is from 0 to12;  and mixtures thereof; R is an axial moiety which mediates thesolubility or substantivity of the singlet oxygen generator wherein R isselected from: a) hydrogen; b) halogen; c) hydroxy; d) C₁-C₂₂ alkyl,C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, ormixtures thereof; e) halogen substituted C₁-C₂₂ alkyl, C₃-C₂₂ branchedalkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof; f)polyhydroxyl substituted C₃-C₂₂ alkyl; g) C₁-C₂₂ alkoxy; h) branchedalkoxy having the formula:

 wherein Z is hydrogen, hydroxyl, C₁-C₃₀ alkyl, C₁-C₃₀ alkoxy, —CO₂H,—OCH₂CO₂H, —SO₃ ⁻M⁺, —OSO₃ ⁻M⁺, —PO₃ ²⁻M, —OPO₃ ²⁻M, or mixturesthereof; M is a water soluble cation in sufficient amount to satisfycharge balance; x is 0 or 1, each y independently has the value from 0to 6, each z independently has the value from 0 to 100; i) substitutedaryl, unsubstituted aryl, or mixtures thereof; j) substitutedalkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; k)substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; l)substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixturesthereof; m) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl,or mixtures thereof; n) C₁-C₂₂ thioalkyl, C₃-C₂₂ branched thioalkyl, ormixtures thereof; o) a carboxylate of the formula:

 wherein R⁹ is: i) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof; ii) halogen substitutedC₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branchedalkenyl, or mixtures thereof; iii) polyhydroxyl substituted C₃-C₂₂alkylene; iv) C₃-C₂₂ glycol; v) C₁-C₂₂ alkoxy; vi) C₃-C₂₂ branchedalkoxy; vii) substituted aryl, unsubstituted aryl, or mixtures thereof;viii) substituted alkylenearyl, unsubstituted alkylenearyl, or mixturesthereof; ix) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; x) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl,or mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstitutedalkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of theformula:

 wherein R¹⁰ and R¹¹ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂alkenyl, C₃-C₂₂ branched alkenyl, or mixtures thereof;  R¹² is: i)hydrogen; ii) C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof;  A is nitrogen or oxygen;X is chlorine, bromine, iodine, or other water soluble anion, v is 0 or1, u is from 0 to 22; q) an amino unit of the formula: —NR¹⁷R¹⁸  whereinR¹⁷ and R¹⁸ are C₁-C₂₂ alkyl, C₃-C₂₂ branched alkyl, C₂-C₂₂ alkenyl,C₃-C₂₂ branched alkenyl, or mixtures thereof; r) an alkylethyleneoxyunit of the formula: —(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z  wherein Z is: i)hydrogen; ii) hydroxyl; iii) —CO₂H; iv) —SO₃ ⁻M⁺; v) —OSO₃ ⁻M⁺; vi)C₁-C₆ alkoxy; vii) substituted aryl, unsubstituted aryl, or mixturesthereof; viii) substituted aryloxy, unsubstituted aryloxy, or mixturesthereof; ix) alkyleneamino; or mixtures thereof;  A is nitrogen oroxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, yis from 0 to 12; s) substituted siloxy of the formula: —OSiR¹⁹R²⁰R²¹ wherein each R¹⁹, R²⁰, and R²¹ is independently i) C₁-C₂₂ alkyl, C₃-C₂₂branched alkyl, C₂-C₂₂ alkenyl, C₃-C₂₂ branched alkenyl, or mixturesthereof; ii) substituted aryl, unsubstituted aryl, or mixtures thereof;iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;iv) an alkylethyleneoxy unit of the formula:—(A)_(v)—(CH₂)_(y)(OCH₂CH₂)_(x)Z;  wherein Z is: a) hydrogen; b)hydroxyl; c) —CO₂H; d) —SO₃ ⁻M⁺; e) —OSO₃ ⁻M⁺; f) C₁-C₆ alkoxy; g)substituted aryl, unsubstituted aryl, or mixtures thereof; h)substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; i)alkyleneamino; or mixtures thereof;  A is nitrogen or oxygen, M is awater soluble cation, v is 0 or 1, x is from 0 to 100, y is from 0 to12; and mixtures thereof, and D is a unit which increases the efficiencyof singlet oxygen production, said unit having the formula —L¹—E or—L¹—B—[L²—E]_(m) wherein E is an aromatic unit having six carbon atoms,provided said E aromatic unit: a) absorbs ultra violet radiation at awavelength of from about 200 nm to about 400 nm; b) has an extinctioncoefficient of at least about 100; and c) has a fluorescence spectrumwhich overlaps the absorption band of said photosensitizer unit; B is abranching unit; and L¹ and L² are linking units, provided said linkingunits when taken together with said B unit comprise a total of at least20 continuous covalent bonds from said P unit to said E units; m is from2 to 4.